Liquid detergent composition

ABSTRACT

STABLE, LIQUID DETERGENT COMPOSITIONS FOR CLEANING SURFACES, SAID COMPOSITIONS CONTAINING PARTICULATE MATERIALS (E.G., ABRASIVES), WATER, ARYLSULFONCHLORAMIDE BLEACHING AGENTS, POTASSIUM IODIDE, ALKYLBENZENESULFONATE DETERGENT, ZWITTERIONIC SYNTHETIC DETERGENT AND ELECTROLYTE, WHICH PREFERABLY COMPRISES A DETERGENCY BUILDER.

"rent Oflice 3,630,922 Patented Dec. 28, 1971 U.S. Cl. 252-99 4 ClaimsABSTRACT OF THE DISCLOSURE Stable, liquid detergent compositions forcleaning surfaces, said compositions containing particulate materials(e.g., abrasives), water, arylsulfonchloramide bleaching agents,potassium iodide, alkylbenzenesulfonate detergent, zwitterionicsynthetic detergent and electrolyte, which preferably comprises adetergency builder.

This application is a continuation-in-part of our copending applicationSer. No. 649,018, filed June 26, 1967 and now abandoned.

CROSS REFERENCE TO RELATED APPLICATIONS Other stable liquid detergentcompositions for cleaning hard surfaces are disclosed in U.S. Patent3,520,818 and the application of Cushman Merlin Cambre, entitled LiquidDetergent Composition, Ser. No. 649,019, filed June 26, 1967.

BACKGROUND OF THE INVENTION This invention relates to liquid detergentcompositions adapted for cleaning hard surfaces and containing ableaching system. More particularly, this invention relates to liquiddetergent compositions containing a stable bleaching system and having ayield value of from about 5 to about 600 dynes per square centimeter.

There has been an increasing demand for bleaching liquid detergentcompositions adapted for cleaning hard surfaces. These liquid detergentcompositions are provided in convenient form and are especiallyformulated for this particular cleaning application. To obtain optimumcleaning and consumer acceptance, these detergent compositions must behomogeneous and easily pourable. These compositions, when intended forthe retail consumer market, should maintain their homogeneity andbleaching effectiveness during ordinary periods of storage and use, andshould have acceptable freeze-thaw char acteristics. It is highlydesirable that liquid detergent compositions for cleaning hard surfacesshould exhibit Bingham plastic characteristics; that is, they shouldexhibit a substantial yield value in order to keep particulate materialfrom settling to the bottom of the container.

When these liquid detergent compositions are intended for industrialapplications, extended product stability, as described above, is not asimportant as it is in the retail consumer market. In industrialapplications, the compositions can be reintegrated and the particulatematerial redistributed before use, for example, by mixing or shaking thecompositions. However, even these products should be stable for at leasta 24-hour period.

It is also very important that the compositions maintain their bleachingeffectiveness during storage.

(A) Yield value The consistency of simple (or Newtonian) liquids is afunction of the nature of the material, temperature, and pressure only.This consistency is known as the "hurt! viscosity coeflicient, absoluteviscosity, or merely viscosity, and is usually measured in centipoises(1 centipoise=0.0l gram/centimeter-second). With a Newtonian liquid, anyforce applied to the system produces some deformation, according to theformula dr ;t

where du/dr=the rate of shear; F=the shear stress, or shearing force perunit area; and p=the viscosity coefiicient.

In the case of non-Newtonian liquids, on the other hand, the consistencyis a function of the material, pressure, temperature, and also the shearstress applied to the system. Those non-Newtonian liquids which areclassified as Bingham plastics, or real plastics, are not'alwaysdeformed when a force is applied to the system. Deformation, if any,takes place according to the formula where p,,=the apparent viscosity,or plastic viscosity, at the shear stress F; f=a characteristic of theliquid called the yield stress, or yield value, measured in units ofpressure; and du/dr and F are as defined above.

If the shear stress applied to the system is less than the yield value,the system will not be deformed at all. Hence, a Bingham plastic systemis capable of supporting indefinitely insoluble particulate materialwhich has a density greater than that of the supporting medium, so longas the material has a particle size and density such that the shearstress which each particle places on the supporting medium does notexceed the yield value.

This is to be contrasted with suspension of heav insoluble particulatematerial in Newtonian liquids with high viscosities. In highly viscousNewtonian liquids, insoluble particulate material is suspended onlybecause the rate of flow is slow. In Bingham plastics, insolubleparticulate material is suspended because the stress imposed by theparticles does not exceed the yield value of the liquid, and therefore,there is no flow at all. Of course, if the yield value of the supportingmedium should sufiiciently decrease for any reason, the particles wouldno longer be suspended. This could be caused, for example, by a physicalor chemical change in the supporting medium. If one of the components ofthe supporting medium is an emulsion which settles into layers uponstanding, the yield value can be lost temporarily; but in such a case,the original composition can be reconstituted by mixing.

"If a chemical reaction either consumes a vital component or produces adamaging one, the loss of yield value can be permanent.

(B) Previous compositions Liquid detergent compositions containing acombina' tion of alkali metal soaps, ethanol amides and potassiumpyrophosphates are known (see U.S. Pat. 3,234,138). Although liquiddetergent compositions containing alkali metal soaps, amides andphosphates exhibit useful properties, these compositions also have somedisadvantageous features. For example, when particulate materials areadded to these compositions and the compositions are then subjected toordinary storage conditions, they may separate into two layers. As theseliquid detergent compositions separate, they lose their ability tosupport particulate material and, accordingly, the particulate materialsettles. As another example, a portion of the amides in thesecompositions is hydrolyzed to soap if the compositions are subjected tohigh storage temperatures, e.g., F. As the amide hydrolyzes, the liquiddetergent characteristics. Again, the particulate material in these 3compositions separate and lose their Bingham plastic compositions isdeposited on the bottom of the respective containers.

A variety of detergent compositions containing synthetic anionicdetergents, soaps, or both, as well as detergency builders andabrasives, are known. See, for example, U.S. Pats. 3,149,078; 3,210,285;3,281,367; Canadian Pats. 635,321 and 685,394. These compositionsusually require the presence of amides, and frequently contain soaps.

Soaps and amides are undesirable in many situations, however. Soapsreact with calcium, magnesium, and other ions present in hard water,forming undesirable scum. Soaps containing about 8 or fewer carbon atomsin their molecular structure act as solubilizing agents, and causemultiple phase systems to lose their Bingham plastic characteristics.Soaps in which the alkyl group is derived from coconut are relativelyexpensive, as compared to alkylbenzenesulfonate synthetic anionicdetergents.

Amides are subject to hydrolysis, especially when compositions arestored at high temperatures, e.g., 110 F. Upon hydrolysis, amides yieldammonium soaps, which are subject to the disadvantages outlined above.For these and other reasons, the use of soaps and amides is to beavoided in practicing the present invention.

Other stable liquid detergent compositions for cleaning hard surfacesare disclosed in U.S. Pat. 3,520,818 and the application of Cushman M.Cambre, Ser. No. 649,019, filed June 26, 1967, for Liquid DetergentComposition. The detergent compositions of U.S. Pat. 3,520,818 are freeof amides, but are required to contain soap. The compositions of U.S.Pat. 3,520,818 also differ in the kind and relative proportions ofcomponents which can be employed.

Accordingly, it is an object of this invention to provide bleachingliquid detergent compositions which exhibit Bingham plasticcharacteristics and which are stable for protracted periods of time. Itis a further object of this Invention to provide bleaching liquiddetergent compositions which remain stable when subjected to bothdepressed and elevated storage temperatures. A still further object ofthis invention is to provide Bingham plastic, bleaching liquid detergentcompositions in which particulate material will not settle to the bottomof the containers when the compositions are stored for protractedperiods of time. Another object of this invention is to providebleaching liquid detergent compositions which exhibit Bingham plasticcharacteristics and which do not contain soaps or amides. It is anotherobject of this invention to provide a bleaching detergent composition inconvenient pourable form. It is yet another object of this invention toprovide a bleaching liquid detergent compositions with good bleachstability.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter. It should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration onlysince various changes and modifications within the spirit and scope ofthis invention will become apparent to those skilled in the art. Allparts, percentages and ratios set forth herein are by weight.

SUMMARY OF THE INVENTION Surprisingly, it has been discovered, accordingto the present invention, that the foregoing objects are obtained withan opaque, liquid, bleaching detergent composition which issubstantially free of soaps, amides and hydrotopes and which has a yieldvalue of from about to about 600 dynes per square centimeter and anapparent viscoscity below about 12,000 centipoises consistingessentially of, by weight of the finished composition.

(1) An anionic alkylbenzenesulfonate synthetic detergent having thegeneral formula:

wherein R is an alkyl chain containing from about 9 to about 15 carbonatoms, and M is a cation selected from the group consisting ofpotassium, sodium, and ammonium cations;

(2) A zwitterionic quaternary ammonio synthetic detergent having thegeneral formula:

wherein R is an alkyl chain containing from about 10 to about 18 carbonatoms; the ratio of alkylbenzenesulfonate detergent to the zwitterionicsynthetic detergent ranges from about 0.4:1 to about 4:1; and thecombined weight of the alkylbenzenesulfonate and zwitterionic syntheticdetergents ranges from about 5% to about 20% by weight of the finishedcomposition;

(3) From 1% to about 60% of an insoluble, particulate material havingparticle diameters ranging from about 1 micron to about 200 microns, anda density of from about 0.5 to about 5.0;

(4) From about 1% to about 10% of polyvalent electrolyte;

(5) From about 1% to about 5% of a bleaching agent having the formulawherein R is a hydrogen atom or short alkyl group containing from 1 toabout 3 carbon atoms and X is selected from the group consisting ofsodium, potassium and chlorine atoms;

(6) From about .1% to about .5% of sodium or potas' sium iodide;

(7) From about 25% to about water; and

(8) Sufficient strong base to adjust the pH of the composition to fromabout 7.5 to about 13.0; wherein said yield value is suflicient tosupport said insoluble particulate material.

DETAILED DESCRIPTION At this juncture, the liquid detergent compositionof this invention will be characterized, in its entirety, in order tofacilitate a better understanding of the individual components and theirfunctions in these liquid detergent compositions.

(A) Yield value It is believed that the supporting medium of the liquiddetergent composition of this invention (that is, the total compositionless the insoluble particulate material) is a suspension which comprisestwo phases. One phase is isotropic and continuous and consists mainly ofinorganic materials such as water, base, and electrolyte. The otherdiscrete phase consists mainly of organic materials such as detergent.The discrete phase is mesomorphic and has a highly oriented physicalstructure. It is apparently this high degree of orientation whichimparts the yield value to the system. The presence of two liquid phasesis possible only in the absence of hydrotropes and other solubiltzingagents. Furthermore, electrolyte is required in the system to salt outthe organic materials from the continuous phase; i.e., to lower thesolubility of the discrete (mainly ogganic) phase in the continuous(mainly inorganic) p ase.

Because it is usually not known whether a system be= haves in a trulyplastic manner at low shear rates, the measurement of exact yield valuesis quite difficult. A close approximation can be obtained by using aBrook field viscometer. The yield value is estimated, in dynes persquare centimeter, by the following relationship;

Yield value viscosit v at. 0.5 r.p.m.-viscosity atl r.p.m.

5 This relationship represents an extrapolation of the shear curve tor.p.m. since an absolute shear stress cannot be measured at 0 r.p.m.

The yield values of the liquid detergent compositions of this inventionrange from about to about 600 dynes per square centimeter. If the yieldvalue is too low, the insoluble, particulate material will not besuspended, because the weight of the individual particles, distributedover the area which supports the particles, will exceed the yield value.However, if the yield value is too great, the composition will becomethick and unmanageable because as the yield value increases, so will theapparent viscosity.

A preferred range of yield values to support the insoluble particulatematerial used in the liquid detergent compositions of this invention isfrom about 100 to about 400 dynes per square centimeter.

(B) Individual components The essential individual components of theliquid detergent composition of this invention are alkylbenzenesulfonatedetergent, zwitterionic synthetic detergent, insoluble particulatematerials, electrolyte, arylsulfonchloramide bleaching agents, sodium orpotassium iodide, and water. Optional components include detergencybuilders, strong base to adjust pH level, and minor ingredients whichhave aesthetic value or which improve the effectiveness of thecomposition. Strong base is not optional, however, if the pH of thedetergent composition without it is below about 7.5. The pH of acomposition of course varies with the identity and relative amounts ofthe components used in it; usually no base is necessary. Thealkylbenzenesulfonate detergent, zwitterionic synthetic detergent, and,if employed the detcrgency builders, are the primary cleaning ordetergent components of this composition.

In preferred embodiments of this invention, abrasives and detergencybuilders, as hereinafter defined, are added to the liquid detergentcomposition of this invention. All of these compositions are capable ofsuspending insoluble particulate materials of the hereinafter specifieddensity and particle size and, accordingly, these particulate materialscan be included as components of these liquid detergent compositions.

( 1) Alkylbenzenesulfonate detergent The alkylbenzenesulfonate detergentused in the liquid detergent compositions has the general formula:

wherein R is an alltyl chain containing from about 9 to about carbonatoms, and M is a cation selected from the group consisting ofpotassium, sodium, ammonium cations; it is preferred that R averageabout 12 carbon atoms and be a normal (straight chain) alkyl group.

From about 2% to about 12% of the above-described alkylbenzenesulfonatedetergent, by weight of the finished detergent composition, is utilizedin the detergent compositions of this invention. It is preferred thatthe finished composition contain from about 2% to about 6%alkylbenzenesulfonate. More important than the amount ofalkylbenzenesulfonate or zwitterionic detergent present individually,however, is the total amount of these two detergents, and the relativeamounts in which they are present, as described below.

(2) zwitterionic synthetic detergent The zwitterionic quaternary ammoniosynthetic detergent of this invention has the following structuralformula:

CH; n -nii-om-om-cmsot wherein R is an alltyl radical containing fromabout 10 to about 18 carbon atoms. It is preferred that R be 6 dodecylor the alltyls derived from coconut fatty alcohol.

The zwitterionic synthetic detergent described above is utilized in thisinvention in amounts of from about 2% to about.14% by weight of thefinished detergent composition. It is preferred that the zwitterionicsynthetic detergent be utilized in amounts of from about 2% to about 7%by weight of the finished composition.

The total amount of alkylbenzenesulfonate and zwitterionic detergentsand the relative amounts in which they are present, are more importantthan the absolute amount of either. While the absolute amount of eachdetergent is of little independent significance, the total amount ofboth detergents determines yield value and ability to dissolve greaseand dirt, and if excessive, makes the detergent composition too thickand unmanageable. The relative amounts of alkylbenzenesulfonate andzwitterionic detergents sharply affect the ability of the system tosupport abrasive. Neither alkylbenzenesulfonate nor zwitterionicsynthetic detergent, alone, will provide a stable support for insolubleparticulate material; how ever, when they are used together as hereindescribed, they cooperate synergistically in a surprising and unexpectedway to provide a stable medium with a yield value that will supportinsoluble particulate material.

The combined weight of alkylbenzenesulfonate and zwitterionic detergentsin the detergent compositions of this invention is from about 5% toabout 20% of the total weight of the finished composition. A preferredembodiment contains from about 5% to about 12% of these detergents.About 6% to about 7% was found to be a level which produxs asufficiently high yield value, but not an unduly thick composition.

Within the preferred range of insoluble particulate material (about toabout see below), it can be further said that between about 10% andabout 18% of the supporting medium (that is, the entire compositionsless suspended insoluble particulate material) should be detergent, andabout 10% to about 16% is preferable. About 12% to about 14% gives thebest-results. At the higher detergent concentrations, the combineddetergent and abrasive make the compositions too thick to be manageable;at the lower detergent concentrations there is not enough detergent toprovide sufficient yield value to support the abrasive. The upper limiton combined detergent and abrasive is a functional one, and is bestexpressed in terms of apparent viscosity. The detergent compositions ofthis invention have an apparent viscosity below about 12,000centipoises; it is preferred that the apparent viscosity be below about10,000. As used here and elsewhere in this specification, apparentviscosity" means the valve obtained with a Brookfield viscometer, ModelLVF, using spindle number 3 at 12 r.p.m. At lower below 40%) abrasiveconcentrations, the concentration of total detergent in the supportingmedium becomes less important, and up to about 20% of the totalcomposition can be detergent.

It is important in the practice of this invention to maintain the weightratio of alkylbenzenesulfonate to zwitterionic synthetic detergent inthe range between from about 0.421 to about 4:1. When thealkylbenzenesulfonate to zwitterionic ratios do not fall within theselimits, the detergent compositions of this invention may haveunacceptably low yield values, or they may separate into two layers atroom temperature, or both. It is preferred that thealkylbenzenesulfonate to zwitterionic synthetic detergent ratio be inthe range of about 0.421 to about 2.0:1. The exact value of this ratiodepends on other materials present in the system. For example, a ratioof about 0.86:1 was found particularly effective for a system containingalkylbenzenesulfonate and zwitterionic detergent, sodium sulfate andsodium chloride.

(3) Insoluble particulate material The insoluble, particulate materialwhich is utilized in this invention can comprise abrasives,bactericides, or

other insoluble, particulate material having a particle size diameterranging from about 1 to about 200 microns and a density of from about0.5 to about 5.0. It is preferred that the diameter of the particlesrange from about 2 microns to about 60 microns and that the densityrange from about 1.0 to about 2.8. The abrasives which can be utilizedin this invention include, but are not limited to, quartz, pumice,pumicite, talc, sili sand, calcium carbonate, china clay, zirconium silate, bentonite, diatomaceous earth, whiting, feldspar, and aluminumoxide. Non-siliceous abrasives and feldspar are preferred for use hereinsince most siliceous abrasives tend to inhibit the removal of aluminummarks. If aluminum oxide is used, the pH of the composition should notbe above about 11, or the aluminum oxide will dissolve. Furthermore, ifa high density abrasive (such as aluminum oxide, pumice containingaluminum oxide, or zirconium silicate) is used, particular care must betaken that the yield value is sufficiently high to support particles ofthe size and density used. For any particular system, the yield valuerequired can be calculated from the density and particle size of thesuspended particles, and from the density of the supporting medium. Theyield value required is equal to the pressure per unit area which theweight of the particle exerts on the supporting medium, taking intoaccount the buoyant force of the supporting medium. For a sphericalparticle of greater density than the supporting medium, this yield valueis given by the formula where f is the yield value in dynes per squarecentimeter, D is the particle diameter in centimeters; g is thegravitational constant, 980.665 centimeters per second per second; a isthe density of the particle to be supported; and d is the density of thesupporting medium (both densities in grams per cubic centimeter). Thistheoretical yield value should be multiplied by a safety factor of about1.5 or 2.0, to take into account such factors as as nonsphericalparticles, inaccuracy in estimating yield value, and occasionalagglomeration of two or more particles, in order to calculate the yieldvalue (as observed) which is necessary to support the particularmaterial which is to be suspended.

In the practice of this invention, from 1% to about 60% of thecomposition of this invention is insoluble particulate material. It ispreferred, however, that from 40% to about 50% by weight of the finishedcomposition be insoluble, particulate material.

(4) Polyvalent electrolyte From about 1% to about 10% of the finishedcomposition is required to be polyvalent electrolyte. For example, from1% to about 10% sodium sulfate can be employed, but from about 2% toabout 3% is preferred, as this allows higher amounts of detergencybuilders to be used. One or more detergency builders can be included inthis electrolyte to serve as a cleaning aid and as a pH buffer. Theamount of detergency builder to be included depends on the particularbuilder used, but in any case should be between and about by weight ofthe finished composition. It is preferred that the total amount ofbuilders be from about 1% to about 7%. Many builders, if present in toogreat a quantity. will cause the system to lose its yield value andsuspending capability.

Tetrapotassium pyrophosphate is preferred to other detergency buildersbecause of its good cleaning characteristics and excellent solubilitycharacteristics. The liquid detergent compositions built withtetrapotassi pyrophosphate also exhibit excellent stabilWEdti? s ics era wt e range of temperatures.

From 0% to about 6% of tetrapotassium pyrophosphate by weight of thefinished detergent composition can be utilized in this invention. Tomaximize stability and optimize the cleaning characteristics of theliquid detergent compositions, about 3% to about 4% tetrapotassiumpyrophosphate should be utilized herein.

Tetraborate can be added to these detergent compositions to improvecleaning (as a detergencvy builder), to improve low temperaturestability properties, and to raise the yield value. The tetraborate canbe introduced into the detergent composition in several forms, e.g.,anhydrous sodium tetraborate, sodium tetraborate pentahydrate, andsodium tetraborate decahydrate. Sodium tetraborate decahydrate ispreferred for use herein as it is readily available to the detergentindustry. When the anhydrous or hydrated tetraborate compounds areutilized, they ionize and tetraborate ions are then present in theseliquid detergent compositions. It has been found that from 0% to about0.8% tetraborate, by weight of the finished detergent composition, canbe utilized in this invention. This range corresponds to 0% to about 2%sodium tetraborate decahydrate by weight of the finished composition.

Other detergency builders which can be employed without destroying theparticle suspending ability of the com position include sodiumtripolyphosphate, Na 0 in an amount ranging from 0% to about 3%, andtrisodium orthophosphate, Na PO in an amount ranging from 0% to about7%. Mixtures of these builders can also be employed.

(5) The bleaching agent The bleaching agent of this invention is anarylsulfonchloramide as described hereinbefore. Specific examplesinclude sodium p-toluenesulfonchloramide, p-toluenesulfondichloramide,sodium, benzenesulfonchloramine, and benzenesulfondichloramide. Thesecompounds are commercially available under the names, respectively, ofChloramine T, Dichloramine T, Chloramine B, and Di chloramine B. Thecorresponding potassium salts are also usable.

(6) The iodide The sodium or potassium iodide is used at very lowlevels, e.g., from about 0.1% to about 0.5% to enhance the bleachingeffectiveness of the bleaching agent. The bleaching agent, by itself, isalmost completely ineftee tive in the compositions of this invention.The potassium iodide is required for proper bleaching effectiveness.

It has been found, surprisingly, that the bleach system of thecompositions of this invention is not stable in the presence ofzwitterionic detergents containing hydroxy groups. Accordingly, it isrequired that the specific zwitterionic detergent claimed herein beused.

(7) Water From about 25% to about of this composition is water. It ispreferred that from about 30% to about 50% by weight of the finishedcomposition be water to optimize yield values and cleaningcharacteristics of the finished product. It is also preferred that softwater be utilized in this invention.

(8) Strong base The pH of the composition is from about 7.5 to about 13,preferably from about 8 to about 11. If necessary, the pH 15 adjusted tothis level by adding a strong base. The most desirable strong bases foruse herein are sodium hy droxide and potassium hydroxide. In thepreferred pH range (about 8 to about 11), the liquid detergentcompositions of this invention have higher yield values and greaterstability, as well as better cleaning capability. Frequently no pHadjustment is required, however, because the builder salts includedraise the pH of the composition to within the desired range.

(9) Minor ingredients Minor amounts of materials which make the COmPUSition of this invention more attractive or more effective can be added ifthey do not significantly alter the excellent tarnish inhibitors such asbenzotriazole or ethylenethiourea, brighteners, iiuorescers, dyes,bluing agents, perfumes, bactericides and corrosion inhibitors.

Hydrotropes such as sodium or potassium xylenesulfonate,toluenesulfonate, or benzenesulfonate, should not be present in thesecompositions. Even very small amounts of these hydrotropes solubilizethe discrete phase into the continuous phase. The detergent composition,thus, becomes a one-phase solution and loses its Bingham plasticcharacteristics with concomitant settling of insoluble, particulatematerial, e.g., abrasive. The composition, in this condition, isaesthetically undesirable and not easily salable on the retail consumermarket or the industrial market.

Also to be avoided are soaps, amides, and other materials which arepresently or potentially solubilizing agents, or which combine withwater hardness ions.

The following example illustrates the present invention.

What is claimed is:

1. A stable, liquid bleaching detergent composition which is free ofsoaps, amides and hydrotropes and which has a yield value of from about5 to about 600 dynes per square centimeter and an apparent viscositybelow about 12,000 centipoises consisting essentially of,

(1) an anionic alkylbenzene sulfonate synthetic detergent having thegeneral formula:

RC H 4O M wherein R is an alkyl chain containing from about 9 to about15 carbon atoms, and M is a cation selected from the group consisting ofpotassium,

sodium and ammonium cations;

(2) a zwitterionic quaternary ammonio synthetic detergent having thegeneral formula:

B'N CH,CH,CH,SO;

a wherein R is an alkyl chain containing from about The followingcompositions were prepared and evalu- 10 to about 18 carbon atoms; theratio of alkylated for bleach stability and yield value.benzenesulfonate detergent to the zwitterionic syn- Calcium 4Quaternary; carbonate tertiary Chlora- Composition LAS 1 HAPS 1 APS H1Oabrasive K4P101 NarSO| amine mine B KI NaOH Percent available chlorineAmount oi 1 week 2 weeks Yield values separation otter 3 days Boom RoomAlter one 7" of sample temperatempera- Composition N aCl 5 CHsOH 1 Asmade week (in.) ture 100 F. ture 100 F 1 0.2 405 270 M 96 07 91 87 2 0.2 1 480 225 36 94 87 88 85 3 8 1 100 I? 91 86 87 82 4 8 02 160 100 B8 6160 39 1 Sodium alkyl (Cu av.) bensenesulionate.

3[N,N-dimethyl-N-allrylammonio]-3-hydroxypropane-l sulionate wherein thealkyl distribution is 0.6%-Cio, 67.6%C

methanol was added to samp es 2 and 3 to show that trace amounts ofmethanol in HAPS were not responsible for the very fllgcific gravity oiabout 2.8 and art cle iameter of about 25 microns.

great bleach loss observed. Sodium chloride was added to sample 3 toshow that NaCl in HAPB was not responsible lor the very great bleachloss observed.

In each case, viscosity data were measured at room temperature (about 74F.), even though the samples may have been stored at higher or lowertemperatures. The viscosities for yield values were read with aBrookfield viscometer, Model RVT, using spindle number C2 at ,6 and 1r.p.m. The apparent viscosities were read with a Brookfield viscometer,Model LVF using spindle number 3 at 12 r.p.m.

The apparent viscosities of compositions l, 2, 3 and 4 were about 1200,about 1200, about 225 and about 400 respectively.

-Thrpis of-compositionrh S-andkwere-all-about 11.5. The correspondingcompositions with the pHs adjusted to about 10.5 are also bleach-stablecompositions having similar yield values.

The following builders can be used in the above examples, alone or incombination, in the amounts indicated, with substantially equivalent orbetter results (and in particular, without destroying the yield valueand ability to suspend particles), provided the level of sodium sulfatedoes not exceed about 3%: tetrapotassium pyrophosphate, 3.5%, as itincreases yield value; sodium tetraborate, 1% (as decahydrate); sodiumtripolyphosphate, 3%; and trisodium phosphate, 5%.

The following can be substituted, with substantially equivalent results,for the calcium carbonate in the above example: quartz, feldspar,silica, pumice, pumicite, talc, china, clay, zirconium silicate,bentonite, diatomaeeous earth, whiting and aluminum oxide, of the sameparticle sizes. By substantially equivalent" results in this and theprevious paragraph, it is meant that stable suspensions with effectivecleaning properties are obtained.

thetic detergent ranges from about 0.4:1 to about 4:1 and the combinedweight of the alkylbenzenesulfonate detergent and the zwitterionicsynthetic detergent ranges from about 5% to about 20% by weight of thefinished composition;

(3) from about 1% to about 60%, by weight of the finished composition,of insoluble, particulate material selected from the group consisting ofquartz, pumice, pumicite, talc, silica sand, calcium carbonate, chinaclay, zirconium silicate, bentonite, diato maceous earth, whiting,feldspar and aluminum oxide, said insoluble particulate material havingparticle diameters ranging from 1 micron to about 200 microns, and adensity from about 0.5 to about 5.0;

(4) from about 1% to about 10%, by weight of the finished composition,of a polyvalent eletcrolyte selected from the group consisting of sodiumsulfate, tetrapotassium pyrophosphate, sodium tetraborate decahydrate,sodium tripolyphosphate, trisodium orthophosphate, sodium tetraboratepentahydrate, and anhydrous sodium tetraborate effective to lower thesolubility and thereby salt out the anioinic alkylbenzene sulfonatesynthetic detergent and the zwitter ionic quaternary ammonio syntheticdetergent from a continuous phase;

(5) from about 1% to about 5%, by weight of the finished composition, ofa bleaching agent having the formula:

wherein R is a hydrogen atom or short alkyl group containing from 1 toabout 3 carbon atoms and X is selected from the group consisting ofsodium, potassium and chlorine atoms;

(6) from about 0.1% to about 0.5%, by weight of the finishedcomposition, of sodium or potassium iodide;

(7) from about 25% to about 85%, by weight of the finished composition,of water; and

(8) sufficient strong base selected from the group consisting of sodiumhydroxide and potassium hydroxide to adjust the pH of the composition tofrom about 7.5 to about 13.0;

said yield value being sufiicient to support said insoluble, particulatematerial; said pH being adjusted to a pH of up to about 11 when saidinsoluble, particulate material is aluminum oxide.

2. The composition of claim 1 wherein the zwitterionic syntheticdetergent is 3-dimethyldodecylaminopropane sulfonate.

3. The composition of claim 1 wherein the alkylbenzenesulfonatedetergent is from about 2% to about 6% by weight of the finisheddetergent composition, the zwitterionic synthetic detergent is fromabout 2% to about 7% by weight of the finished detergent composition,the ratio of alkylbenzenesulfonate detergent to zwitterionic detergentis from about 0.4:1 to about 20:1, and the total amount ofalkylbenzenesulfonate and zwitter- References Cited UNITED STATESPATENTS 3,042,622 7/1962 Kirschenbauer 252--99 3,149,078 9/1964 Zmode252-99 X 3,346,873 10/1967 Herrmann 282152 X 3,351,557 1/1967 Almsteadet al. 252152 X 3,453,144 7/1969 Morgan et al 252-140 X FOREIGN PATENTS832,105 4/1960 Great Britain 252-99 1,447,747 6/1966 France 252-1521,484,489 5/1967 France 252-152 MAYER WEINBLATT, Primary Examiner U.S,C1.X.Ra

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